This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-319800, filed Nov. 10, 1999, the entire contents of which are incorporated herein by reference.
The present invention relates to a silver halide color reversal photographic lightsensitive material, hereinafter photographic lightsensitive material is also referred to as xe2x80x9cphotosensitive materialxe2x80x9d, and a color image forming method using the same.
Color reversal films are transmitting materials, have high picturing capacity and good color reproduction resulting from a wide density dynamic range (common color reversal films are designed to have a transmission density of 3.0 or more in standard processing), and have high resolving power based on high graininess-sharpness. Hence, color reversal films are extensively used in various purposes from printing to color photographs requiring high quality. A development process of color reversal film photosensitive materials includes first developmentxe2x80x94reversal processingxe2x80x94color development, and a subsequent desilvering step. Compared to other color image forming methods (e.g., color paper and color negative films), the replenisher volume of a processing solution in the development step is larger, and the time of this processing step is longer.
To reduce the development time (e.g., the time of color development), a silver halide must be developed faster. However, the development rate of a silver halide is roughly determined by its halogen composition. Also, this halogen composition is determined in accordance with the sensitivity or the ease of spectral sensitization or in order to use the interimage effect produced in development. Therefore, the development rate of a silver halide cannot be easily changed.
One obstacle to shortening the color development time is that the maximum density of cyan lowers when the color development time is shortened. As a countermeasure against this problem, Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-)63-285548 has disclosed a method of reducing the color development time by the use of a photosensitive material in which the silver coating amount is 3.5 to 12 g per m2 of the material and a silver halide emulsion in each low-speed layer is a monodisperse emulsion.
The present inventors made extensive studies on methods of reducing the color development time including this method disclosed in JP-A-63-235548, and have found that another approach required for recent development processing is to reduce the replenishment of a developer, and that when the replenishment rate of a color developer is reduced the color development time cannot be shortened only by the use of monodisperse emulsions as disclosed in JP-A-63-285548. This is a problem still difficult to solve. Another problem when the color development time is shortened is that uneven color generation produced in the processing step worsens. The method disclosed in JP-A-63-295548 cannot well improve this problem. Hence, the color development time is difficult to reduce also in respect of processing nonuniformity.
It is an object of the present invention to provide a color reversal photosensitive material suitable for reducing the time or replenishment amount of a development step and having small processing nonuniformity, and a color image forming method using the same.
The object of the present invention was achieved by the following photosensitive materials.
(1) A silver halide color reversal photosensitive material comprising at least one blue-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one red-sensitive emulsion layer on a transparent support, and capable of forming a color image when the photosensitive material was subjected to color development in the presence of an aromatic primary amine color developing agent after the photosensitive material was subjected to first development of black-and-white development, wherein the silver halide content in the photosensitive material before the first development is 2.5 to 6.0 g in terms of silver per m2 of the photosensitive material, the silver halide content in an unexposed portion of the photosensitive material immediately before the color development is 1.0 to 2.5 g in terms of silver per m2 of the photosensitive material, and the maximum density of each of cyan, magenta, and yellow in the color image after the color development is 3.0 or more.
(2) The color reversal photosensitive material described in item (1) above, wherein at least one of the green- and red-sensitive emulsion layers contains a 2-equivalent coupler, and the molar ratio of this 2-equivalent coupler to all image-forming couplers contained in the photosensitive emulsion layer is 30% to 100%.
(3) The color reversal photosensitive material described in item (1) above, wherein the photosensitive material contains at least one magenta coupler represented by formula (MC-I) below or at least one cyan coupler represented by formula (CC-I) below, and the molar ratio of the coupler to all image-forming couplers in the photosensitive emulsion layer containing the magenta coupler or the cyan coupler is 30% to 100%. 
wherein R1 represents a hydrogen atom or a substituent; one of G1 and G2 represents a carbon atom, the other represents a nitrogen atom; and R2 represents a substituent and bounds to one of G1 and G2 which is a carbon atom. R1 and R2 can further have a substituent. A polymer of formula (MC-I) can be formed via R1 or R2, or the coupler represented by formula (MC-I) can be bonded to a polymeric chain via R1 or R2. X represents a hydrogen atom or a group which splits off by a coupling reaction with an oxidized form of the aromatic primary amine color developing agent. 
In formula (CC-I), Ga represents xe2x80x94C(R13)xe2x95x90 or xe2x80x94Nxe2x95x90, provided that when Ga represents xe2x80x94Nxe2x95x90, Gb represents xe2x80x94C(R13)xe2x95x90, and when Ga represents xe2x80x94C(R13)xe2x95x90, Gb represents xe2x80x94Nxe2x95x90. R13 represents a substituent.
Each of R11 and R12 represents an electron attracting group having a Hammett substituent constant "sgr"p value of 0.20 to 1.0. Y represents a hydrogen atom or a group which splits off by a coupling reaction with the oxidized form of the aromatic primary amine color developing agent.
(4) A color image forming method comprising a step of black-and-white development, a step of reversal processing and then a step of color development, wherein the photosensitive material described in one of items (1) to (3) above is subjected to the step of color development with a development time of 1 to 5 min.
(5) A color image forming:method comprising a step of black-and-white development, a step of reversal processing and then a step of color development, wherein the photosensitive material described in one of items (1) to (3) above is subjected to the step of color development in which a replenishment amount of a color developer is set to 1.0 L or less per m2 of a processing area of the photosensitive material.
The present invention will be described in detail below.
The silver halide color reversal photosensitive material of the present invention has the maximum density of each of yellow, magenta, and cyan of a color image of 3.0 or more. This determination of the density is done by performing Development Process A described in Example 1 of the specification to an unexposed photosensitive material and measuring the color image density (status A) after the processing. The Development Process A in the determination is conducted after running is performed with a photosensitive material to be determined whose 40% in an area ratio was fully exposed to light, until the replenishment amount of the first development becomes three times the tank volume.
A feature of the photosensitive material of the present invention is that the content of a silver halide before the first development is 2.5 to 6.0 g in terms of silver per m2 of the material. Another feature of the photosensitive material of the invention is that the silver halide content in an unexposed portion of the material after the black-and-white development and the reversal processing and immediately before the color development is 1.0 to 2.5 g in terms of silver per m2 of the material.
These silver halide contents in terms of silver amounts are obtained as follows.
Three same photosensitive materials are prepared, and each photosensitive material is subjected to silver amount measurements (i), (ii) to (iv), and (v) to (viii) below, respectively. (Silver halide content before first development)
The following processing is performed at 38xc2x0 C. except for a drying step.
(i) The amounts of all silver compounds such as a silver halide and metal silver contained in a first unexposed photosensitive material are obtained by a fluorescence x-ray method (a silver amount A).
(ii) A second photosensitive material that remains unexposed is fixed by a fixer having the following formulation and subsequently washed with water.
 less than Fixer greater than 
The pH is adjusted by acetic acid or ammonia water.
The processing time is 4 min, and then, the processed material is washed with running water for 4 min, and dried (at 50xc2x0 C. for 30 min).
(iii) The silver amount contained in the photosensitive material thus processed in accordance with (ii) is measured as in the above item (i) (a silver amount B). (
iv) (Silver amount A)-(silver amount B) is defined as the content (in terms of silver amount) of a silver halide before first development. (Silver halide content in an unexposed portion immediately before color development)
(v) A third photosensitive material that remains unexposed is processed as follows.
 less than First Developer; Processing Time 6 Min greater than 
The pH is adjusted by sulfuric acid or potassium hydroxide.
 less than Washing; Processing Time 2 Min greater than 
 less than Reversal Solution; Processing Time 2 Min greater than 
The pH is adjusted by acetic acid or sodium hydroxide.
 less than Washing; Processing Time 2 Min greater than 
(vi) The thus processed third material is desilvered by the same fixer as in the above item (ii).
(vii) The silver amount of the thus desilvered material is measured as in the above item (iii) (a silver amount C).
(viii) (Silver amount A)-(silver amount C) is defined as the silver halide content (in terms of silver amount) at an unexposed portion immediately before color development.
The silver halide content immediately before color development of the photosensitive material of the present invention is 1.0 to 2.5 g, preferably 2.3 g or less, and more preferably, 2.1 g or less in terms of silver per m2 of the material.
Also, the silver halide content of the photosensitive material before first development of the present invention is 2.5 to 6.0 g, preferably 2.5 to less than 4.0 g, and more preferably, 2.5 to less than 3.5 g in terms of silver per m2 of the material.
In the present invention, it is preferable that the silver halide content of the photosensitive material before first development is 2.5 to less than 4.0 g in terms of silver per m2 of the material, and the silver halide content in an unexposed portion immediately before color development is 2.3 g or less in terms of silver per m2 of the material. The silver halide content in an unexposed portion immediately before color development is more preferably 40% to 75% of the silver halide content before first development.
In the present invention, means for achieving the silver halide content in the photosensitive material before first development and the silver halide content in an unexposed portion immediately before color development described above can be any means.
In a common color reversal photosensitive material, fog occurs in first development even in an unexposed portion. The relationship between the silver halide amounts specified in the present invention can be met by controlling the coating amounts of silver halide emulsions and the degree of this fog.
An example of a method of increasing the amount of fog in first development is to add colloidal silver grains or previously fogged silver halide grains to a photosensitive emulsion layer or a non photosensitive interlayer.
In the present invention, it is preferable to add colloidal silver grains or previously fogged silver halide grains to a photosensitive emulsion layer.
The colloidal silver that is capable of using can be prepared by methods described in, e.g., U.S. Pat. Nos. 2,688,601 and 3,459,563. The colloidal silver that is capable of using in the present invention can have any color such as yellow, red, or black. When the colloidal silver is added to a photosensitive emulsion layer, the silver molar ratio of the colloidal silver to a silver halide contained in the photosensitive emulsion layer is preferably 0.01% to 10%, and more preferably, 0.05% to 5%. When the colloidal silver is added to an interlayer, the silver molar ratio of the colloidal silver to a silver halide in a photosensitive emulsion layer directly adjacent to the interlayer is preferably 0.1% to 30%, and more preferably, 0.5% to 20%.
In the present invention, the use of previously fogged silver halide grains is also preferred. A previously fogged silver halide emulsion grain is a silver halide emulsion grain whose interior or surface is previously fogged, and is a non photosensitive silver halide grain which can be developed non-imagewise regardless of whether a photosensitive material is unexposed or exposed. When the previously fogged silver halide emulsion grains are added to a photosensitive emulsion layer, the silver molar ratio of the grains to a silver halide contained in the photosensitive emulsion layer is preferably 1% to 30%, and more preferably 3% to 15%. When the previously fogged silver halide emulsion grains are added to an interlayer, the silver molar ratio of the grains to a silver halide in a photosensitive emulsion layer directly adjacent to the interlayer is preferably 5% to 50% and, more preferably, 10% to 30%.
The surface-fogged silver halide emulsion that is capable of using in the present invention can be prepared by a method of adding a reducing agent or gold salt to an emulsion capable of forming a surface latent image at an appropriate pH and pAg, a method of heating at a low pAg, or a method of giving uniform exposure. Examples of the reducing agent are stannous chloride, a hydrazine compound, and ethanol amine.
In the surface-fogged emulsion, any silver halide such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver bromochloroiodide can be used. In the present invention, however, silver iodobromide or silver bromochloroiodide is preferred. Although the grain size is not particularly limited, an average grain size, which is an equivalent sphere diameter, is preferably 0.01 to 0.75 xcexcm, and particularly preferably, 0.05 to 0.6 xcexcm.
An internally fogged silver halide emulsion grain is a core-shell type grain consisting of a surface-fogged silver halide core and a silver halide shell covering the surface of the core.
In the present invention, the use of surface-fogged silver halide emulsion grains is preferred.
In the present invention, more favorable results are obtained when colloidal silver is used than when fogged silver halide emulsion grains are used. It is also preferable to add colloidal silver grains to a photosensitive emulsion layer.
In the present invention, any coupler can be used provided that a color image having a maximum density of 3.0 or more is given, and an arbitrary coupler coating amount can be selected. However, a coupler by which the density of a formed dye per mol of silver is low increases the coating amount thereof and deteriorates the sharpness or the physical strength of the photosensitive material. Therefore, it is preferable to use a magenta coupler and cyan coupler meeting at least one of the following requirements:
(i) Two-equivalent coupler,
(ii) Magenta coupler represented by formula (MC-I), and
(iii) Cyan coupler represented by formula (CC-I).
In particular, at least one magenta coupler represented by formula (MC-I) or at least one cyan coupler represented by formula (CC-I) is preferably contained. It is more preferable that at least one magenta coupler represented by formula (MC-I) and at least one cyan coupler represented by formula (CC-I) are contained.
Couplers preferably used in the present invention will be described in more detail below.
First, 2-equivalent couplers will be explained.
2-equivalent cyan couplers and 2-equivalent magenta couplers preferably used in the present invention can be any couplers as long as they are 2-equivalent couplers.
A 2-equivalent coupler is a coupler whose coupling position is substituted by a group which can split off as an anion by a coupling reaction with the oxidized form of an aromatic primary amine color developing agent.
Examples of 2-equivalent magenta couplers favorable to the present invention are 2-equivalent couplers of couplers represented by formula (2M-I) below and formula (MC-I) to be described later. Examples of 2-equivalent cyan couplers favorable to the present invention are 2-equivalent couplers of couplers represented by formula (2C-I) or (2C-II) below and formula (CC-I) to be described later. 
Formula (2M-I) will be described first. In formula (2M-I), Ar represents a substituted or nonsubstituted phenyl group, B represents a substituent, Y1 represents a group which can split off as an anion by a coupling reaction with the oxidized form of an aromatic primary amine color developing agent.
Examples of a split-off group represented by Y1 are groups, except for a hydrogen atom, enumerated in the explanation of X in formula (MC-I) to be described later. Y1 is preferably an arylthio group or a nitrogen-containing heterocyclic group which bonds to the coupling position by a nitrogen atom. Y1 is more preferably a substituted or nonsubstituted phenylthio group, substituted or nonsubstituted pyrazole, 1,2,4-triazole, or 1,2,3-triazole group.
Ar represents a substituted or nonsubstituted phenyl group. Ar is preferably a nonsubstituted phenyl group or a phenyl group substituted by at least one chlorine atom or fluorine atom. Ar is more preferably a phenyl group substituted by two or three chlorine atoms or fluorine atoms.
B represents a substituent. Examples are groups enumerated as examples of R2 in formula (MC-I) to be described later. B is preferably an anilino group or acylamino group, and more preferably, an anilino group or acylamino group having a total number of carbon atoms of 10 to 50.
Practical compound examples of a coupler represented by formula (2M-I) will be presented below. However, the present invention is not limited to these examples. 
Formula (2C-I) will be described next.
In formula (2C-I), Y2 represents a split-off group. Examples are those, except for a hydrogen atom, enumerated in the explanation of X in formula (MC-I) to be described later. In formula (2C-I), Y2 is preferably a halogen atom, alkylthio group, arylthio group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, or arylcarbonyloxy group, more preferably, a halogen atom, and most preferably, a chlorine atom.
A1 represents a substituent selected from an acyl group, acyloxy group, and acylamino group. These substituents can further have a substituent. A1 is preferably an acyl group or acylamino group, and more preferably, an acylamino group,
A2 represents a hydrogen atom or substituent. Examples of the substituent are those enumerated as examples of R2 in formula (MC-I) to be described later. A2 is preferably a hydrogen atom or halogen atom, and a chlorine atom is preferable as a halogen atom.
A3 represents a substituent. Examples are those enumerated as examples of R2 in formula (MC-I) to be described later. A3 is preferably an alkyl group, acylamino group, alkoxycarbonylamino group, or carbamoyloxy group.
A preferred example of a coupler represented by formula (2C-I) is a coupler in which A1 is an acylamino group substituted by at least two fluorine atoms, A2 is a hydrogen atom, A3 is an acylamino group or carbamoyloxy group each having a total number of carbon atoms of 10 to 50, and Y2 is a chlorine atom, or a coupler in which A1 is an acylamino group having a total number of carbon atoms of 10 to 50, A2 is a chlorine atom, A3 is a 1- to 3-carbon alkyl group, and Y2 is a chlorine atom.
Practical examples of a coupler represented by formula (2C-I) will be presented below. However, the present invention is not limited to these examples. 
Formula (2C-II) will be described below.
In formula (2C-II), Y3 represents a group which can split off by a coupling reaction with the oxidized form of an aromatic primary amine color developing agent. Examples of this split-off group are those, except for a hydrogen atom, enumerated in the explanation of X in formula (MC-I) to be described later. In formula (2C-II), Y3 is preferably a halogen atom, alkylthio group, arylthio group, alkoxy group, aryloxy group, acyloxy group, or carbamoyloxy group, more preferably, a halogen atom, alkoxy group, alkylthio group, or acyloxy group, and most preferably, a chlorine atom, alkoxy group, or acyloxy group.
A4 represents a substituent. Examples are those enumerated as examples of R2 in formula (MC-I) to be described later. A4 is preferably a carbamoyl group, acylamino group, alkoxycarbonyl group, or acyl group, and most preferably, an carbamoyl group. A4 is preferably a group having a total number of carbon atoms of 8 to 60 and gives immobility to the coupler represented by formula (2C-II).
A5 represents a hydrogen atom or substituent. Examples of the substituent are those enumerated as examples of R2 in formula (MC-I) to be described later. A5 is preferably a hydrogen atom, acylamino group, alkoxycarbonylamino group, ureido group, or sulfonylamino group, and more preferably, a hydrogen atom, acylamino group, alkoxycarbonylamino group, or aminocarbonylamino group.
Practical examples of a coupler represented by formula (2C-II) will be presented below. However, the present invention is not restricted to these examples. 
(ii) Magenta coupler represented by formula (MC-I)
Formula (MC-I) will be described below.
In formula (MC-I), R1 represents hydrogen atom or a substituent selected from an alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, arylthio group, alkylthio group, ureido group, alkoxycarbonylamino group, carbamoyloxy group, and heterocyclic thio group. These substituents can further have a substituent.
Examples of the substituent represented by R1 are an alkyl group (e.g., methyl, ethyl, isopropyl, t-butyl, t-amyl, adamantyl, 1-methylcylopropyl, t-octyl, cyclohexyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-di-t-amylphenoxy)propyl); aralkyl group (e.g., benzyl, 4-methoxybenzyl, and 2-methoxybenzyl); aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, and 4-tetradecanamidophenyl); alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy, and 2-phenoxyethoxy); aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamoylhpenoxy); amino group (including an anilino group; e.g., methylamino, ethylamino, anilino, dimethylamino, diethylamino, t-butylamino, 2-methoxyanilino, 3-acetylaminoanilino, and cyclohexylamino); acylamino group (e.g., acetamide, benzamide, tetradecaneamide, 2-(2,4-di-t-amylphenoxy)butaneamide, 4-(3-t-butyl-4-hydroxyphenoxy)butaneamide, and 2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decanamide); ureido group (e.g., phenylureido, methylureido, and N,N-dibutylureido); alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3-(4-t-butylphenoxy)propylthio); arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, and 4-tetradecanamidophenylthio); alkoxycarbonylamino group (e.g., methoxycarbonylamino and tetradecyloxycarbonylamino); carbamoyloxy group (e.g., N-methylcarbamoyloxy and N-phenylcarbamoyloxy); and heterocyclic thio group (e.g., 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio).
Of these substituents, an alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, and amino group are preferred, a secondary or tertiary alkyl group having a total number of carbon atoms of 3 to 15 is more preferred, and a 4- to 10-carbon, tertiary alkyl group is most preferred.
X represents a hydrogen atom or a split-off group which can split off by a coupling reaction with the oxidized form of an aromatic primary amine color developing agent. Examples of the split-off group are a halogen atom, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy or arylsulfonyloxy group, acylamino group, alkylsulfonamide or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylthio, arylthio, or heterocyclic thio group, carbamoylamino group, carbamoyloxy group, 5- or 6-membered, nitrogen-containing heterocyclic group, imide group, and arylazo group. These groups can be further substituted by groups enumerated as substituents of R2.
More specifically, examples of X are a halogen atom (e.g., a fluorine atom, chlorine atom, and bromine atom); alkoxy group (e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, and ethoxycarbonylmethoxy); aryloxy group (e.g., 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 4-methoxycarboxyphenoxy, 4-carbamoylphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, and 2-carboxyphenoxy); acyloxy group (e.g., acetoxy, tetradecanoyloxy, and benzoyloxy); alkylsulfonyloxy or arylsulfonyloxy group (e.g., methanesulfonyloxy and toluenesulfonyloxy); acylamino group (e.g., dichloroacetylamino and heptafluorobutylylamino), alkylsulfonamide or arylsulfonamide group (e.g., methanesulfonamino, trifluoromethanesulfonamino, and p-toluenesulfonylamino); alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy and benzyloxycarbonyloxy); aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy); alkylthio, arylthio, or heterocyclic thio group (e.g., dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and tetrazolylthio); carbamoylamino group (e.g., N-methylcarbamoylamino and N-phenylcarbamoylamino); carbamoyloxy group (e.g., N,N-dimethylcarbamoyloxy, N-phenylcarbamoyloxy, morpholinylcarbamoyloxy, and pyrrolidinylcarbamoyloxy); 5- or 6-membered, nitrogen-containing heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and 1,2-dihydro-2-oxo-1-pyridyl); imide group (e.g., succinimide and hydantoinyl); and arylazo group (e.g., phenylazo and 4-methoxyphenylazo). X can also take the form of a bis coupler obtained by condensing a 4-equivalent coupler by aldehydes or ketones, as a split-off group bonded via a carbon atom.
X is preferably a hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylthio or arylthio group, or 5- or 6-membered, nitrogen-containing heterocyclic group which bonds to the coupling active position by a nitrogen atom, and particularly preferably, a hydrogen atom, chlorine atom, or phenoxy group which may be substituted.
One of G1 and G2 is a nitrogen atom, and the other is a carbon atom. R2 in formula (MC-I) bonds to one of G1 and G2 which is a carbon atom.
R2 represents a substituent. Examples are a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, and azolyl group. These substituents can have a substituent.
More specifically, examples of a substituent represented by R2 are a halogen atom (e.g., a chlorine atom and bromine atom); alkyl group (e.g., a 1- to 32-carbon, straight-chain or branched-chain alkyl group and cycloalkenyl group; more specifically, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamid o}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-di-t-amylphenoxy)propyl); aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, and 4-tetradecanamidophenyl); heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl); cyano group; hydroxyl group; nitro group; carboxyl group; amino group; alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, and 2-methanesulfonylethoxy); aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamoylphenoxy); acylamino group (e.g., acetamide, benzamide, tetradecanamide, 2-(2,4-di-t-amylphenoxy)butaneamide, 4-(3-t-butyl-4-hydroxyphenoxy)butaneamide, 2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide); alkylamino group (e.g., methylamino, butylamino, dodecylamino, diethylamino, and methylbutylamino); anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, and 2-chloro-5-{xcex1-(3-t-butyl-4-hydroxyphenoxy) dodecaneamido}anilino); ureido group (e.g., phenylureido, methylureido, and N,N-dibutylureido); sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino); alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3-(4-t-butylphenoxy)propylthio); arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, and 4-tetradecanamidophenylthio); alkoxycarbonylamino group (e.g., methoxycarbonylamino and tetradecyloxycarbonylamino); sulfonamide group (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-methyloxy-5-t-butylbenzenesulfonamide); carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, and N-(3-(2,4-di-t-amylphenoxy)propyl)carbamoyl); sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl); sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, and toluenesulfonyl); alkoxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, and octadecyloxycarbonyl); heterocyclic oxy group (e.g., 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy); azo group (e.g., phenylazo, 4-methoxphenylazo, 4-pyvaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo); acyloxy group (e.g., acetoxy); carbamoyloxy group (e.g., N-methylcarbamoyloxy and N-phenylcarbamoyloxy); silyloxy group (e.g., trimethylsilyloxy and dibutylmethylsilyloxy); aryloxycarbonylamino group (e.g., phenoxycarbonylamino); imide group (e.g., N-succinimide, N-phthalimide, and 3-octadecenylsuccinimide); heterocyclic thio group (e.g., 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-trizole-6-thio, and 2-pyridylthio); sulfinyl group (e.g., dodecanesulfinyl, 3-pentadecylphenylsulfinyl, and 3-phenoxypropylsulfinyl); phosphonyl group (e.g., phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl); aryloxycarbonyl group (e.g., phenoxycarbonyl); acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl); and azolyl group (e.g., imidazolyl, pyrazolyl, 3-chloro-pyrazole-1-yl, and triazole).
In a case where a group represented by R2 can further have a substituent, such further substituent may be an organic substituent which bonds to R2 with a carbon atom, oxygen atom, nitrogen atom, or sulfur atom thereof, or a halogen atom.
Preferable examples of R2 are an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, alkoxycarbonylamino group, and acylamino group. More preferably, R2 is a group having a total number of carbon atoms of 6 to 70, which contains a 6- to 70-carbon alkyl group or aryl group as a partial structure, and gives immobility to a coupler represented by formula (MC-1).
The coupler represented by formula (MC-1) is preferably those where R2 is a group represented by formula (BL-1) or (BL-2) below: 
In formula (BL-1), each of R3, R4, R5, R6, and R7 independently represents a hydrogen atom or substituent, and at least one of them represents a substituent having a total number of carbon atoms of 4 to 70 and containing a substituted or nonsubstituted alkyl group as a partial structure, or a substituent having a total number of carbon atoms of 6 to 70 and containing a substituted or nonsubstituted aryl group as a partial structure. The term xe2x80x9cas a partial structurexe2x80x9d herein includes such a group is attached to each of R3 to R7 as a substituent, and also such a group itself is each of R3 to R7. Accordingly, each of R3 to R7 itself may be an alkyl group having a total number of carbon atoms of 4 to 70, or an aryl group having a total number of carbon atoms of 6 to 70.
A group represented by formula (BL-1) will be described below. Each of R3, R4, R5, R6, and R7 independently represents a hydrogen atom or substituent. Examples of this substituent are those enumerated above for R2. At least one of R3, R4, R5, R6, and R7 is a substituent having a total number of carbon atoms of 4 to 70 and containing a substituted or nonsubstituted alkyl group as a partial structure, or a substituent having a total number of carbon atoms of 6 to 70 and containing a substituted or nonsubstituted aryl group as a partial structure. Preferable examples are an alkoxy group, aryloxy group, acylamino group, ureido group, carbamoyl group, alkoxycarbonylamino group, sulfonyl group, sulfonamide group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, alkyl group, and aryl group each having a total number of carbon atoms of 4 (6 if an aryl group is contained) to 70, and each containing a substituted or nonsubstituted alkyl or aryl group as a partial structure. Of these substituents, a 4- to 70-carbon alkyl group and an alkoxy group, acylamino group, and sulfonamide group containing a 4- to 70-carbon alkyl group as a partial structure are preferred.
In particular, R3 or both of R4 and R6 are preferably the above mentioned substituents containing a substituted or nonsubstituted alkyl or aryl group as a partial structure, and having a total number of carbon atoms of 4 (6 if an aryl group is contained as the partial structure) to 70.
In formula (BL-2), G3 represents a substituted or nonsubstituted methylene group, a represents an integer from 1 to 3, R8 represents a hydrogen atom, alkyl group, or aryl group, G4 represents xe2x80x94COxe2x80x94 or xe2x80x94SO2xe2x80x94, and R9 represents a substituent having a total number of carbon atoms of 6 to 70 and containing a substituted or nonsubstituted alkyl or aryl group as a partial structure. If R9 has a substituent, examples of this substituent are those enumerated above for R2. If a is 2 or more, a plurality of G3""s may be the same or different. Preferably, a group represented by (G3)a is xe2x80x94CH2xe2x80x94, xe2x80x94C2H4xe2x80x94, xe2x80x94C(CH3)Hxe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94C(CH3)Hxe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94C(CH3)Hxe2x80x94, xe2x80x94C(CH3)Hxe2x80x94C(CH3)Hxe2x80x94, or xe2x80x94C(CH3)2xe2x80x94C(CH3)2xe2x80x94, R8 is a hydrogen atom, G4 is xe2x80x94COxe2x80x94 or xe2x80x94SO2xe2x80x94, and R9 is a substituted or nonsubstituted alkyl or aryl group each having a total number of carbon atoms of 10 to 70.
In a compound represented by formula (MC-1), if G1 is a nitrogen atom, G2 is a carbon atom, and x is a hydrogen atom, it is desirable that R1 be a tertiary alkyl group, R2 be a group represented by formula (BL-1), and each of R4 and R6 be a group selected from an acylamino group, sulfonamide group, ureido group, alkoxycarbonylamino group, sulfonyl group, carbamoyl group, sulfamoyl group, sulfamoylamino group, and alkoxycarbonyl group, each of which is substituted by a substituted or nonsubstituted alkyl group having a total number of carbon atoms of 4 or more or by a substituted or nonsubstituted aryl group having a total number of carbon atoms of 6 or more.
In a compound represented by formula (MC-I), if G1 is a carbon atom, G2 is a nitrogen atom, and x is a hydrogen atom, R1 is preferably a tertiary alkyl group, and R2 is preferably a group represented by formula (Bl-1) or (BL-2), and particularly preferably, a group represented by formula (BL-2).
In a compound represented by formula (MC-I), if G1 is a nitrogen atom, G2 is a carbon atom, and x is a split-off group except for a hydrogen atom, it is favorable that R1 be a tertiary alkyl group, R2 be a group represented by formula (BL-1), R3 be a group selected from an acylamino group, sulfonamide group, ureido group, alkoxycarbonylamino group, sulfonyl group, carbamoyl group, sulfamoyl group, sulfamoylamino group, and alkoxycarbonyl group, each of which is substituted by a substituted or nonsubstituted alkyl group having a total number of carbon atoms of 4 or more or by a substituted or nonsubstituted aryl group having a total number of carbon atoms of 6 or more, and X is a chlorine atom.
In a compound represented by formula (MC-I), if G1 is a carbon atom, G2 is a nitrogen atom, and X is a substituent except for a hydrogen atom, R1 is preferably a tertiary alkyl group, and R2 is preferably a group represented by formula (Bl-1) or (BL-2), and particularly preferably, a group represented by formula (BL-2).
In the present invention, it is desirable that G1 be a carbon atom, G2 be a nitrogen atom, R1 be a tertiary alkyl group, and R2 be represented by formula (BL-2) in which G4 is xe2x80x94SO2xe2x80x94, R9 is a phenyl group having at least one group, which contains a 6- to 50-carbon alkyl group, as a substituent, and a is 1 or 2, and it is particularly desirable that X be a hydrogen atom, chlorine atom, or substituted phenyloxy group.
Practical compound examples of formula (MC-I) will be presented below. However, the present invention is not limited to these examples.
A coupler represented by formula (MC-1) of the present invention can be synthesized by know methods. Examples are described in U.S. Pat. Nos. 4,540,654, 4,705,863, and 5,451,501, JP-A""s-61-65245, 62-209457, 62-249155, and 63-41851, Jpn. Pat. Appln. KOKOKU Publication No. (hereinafter referred to as JP-B-)7-122744, JP-B""s-5-105682, 7-13309, and 7-82252, U.S. Pat. Nos. 3,725,067 and 4,777,121, JP-A""s-2-201442, 2-101077, 3-125143, and 4-242249.
(iii) A coupler represented by formula (CC-I) will be described below.
In formula (CC-I), Ga represents xe2x80x94C(R13)xe2x95x90 or xe2x80x94Nxe2x95x90. When Ga represents xe2x80x94Nxe2x95x90, Gb represents xe2x80x94C(R13)xe2x95x90. When Ga represents xe2x80x94C(R13)xe2x95x90, Gb represents xe2x80x94Nxe2x95x90.
Each of R11 and R12 represents an electron attractive group having a Hammett substituent constant "sgr"p value of 0.20 to 1.0. The sum of the "sgr"p values of R11 and R12 is desirably 0.65 or more. The coupler of the present invention is given superior performance as a cyan coupler by introducing this strong electron attractive group. The sum of the "sgr"p values of R11 and R12 is preferably 0.70 or more, and its upper limit is about 1.8.
In the present invention, each of R11 and R12 is an electron attractive group with a Hammett substituent constant "sgr"p value (to be simply referred to as a "sgr"p value hereinafter) of 0.20 to 1.0, preferably an electron attractive group having a "sgr"p value of 0.30 to 0.8. The Hammett""s rule is an empirical rule proposed by L. P. Hammett in 1935 in order to quantitatively argue the effects of substituents on reaction or equilibrium of benzene derivatives. The rule is widely regarded as appropriate in these days. The substituent constants obtained by the Hammett rule include a "sgr"p value and a "sgr"m value, and these values are described in a large number of general literature. For example, the values are described in detail in J. A. Dean ed., xe2x80x9cLange""s Hand Book of Chemistry,xe2x80x9d the 12th edition, 1979 (McGraw-Hill), xe2x80x9cThe Extra Number of The Domain of Chemistry,xe2x80x9d Vol. 122, pages 96 to 103, 1979 (Nanko Do) and Chemical Reviews, vol. 91, pp.165-195 (1991). In the present invention, each of R11 and R12 is defined by the Hammett substituent constant "sgr"p value. However, this does not mean that R11 and R12 are limited to substituents having the already known values described in these literature. That is, the present invention includes, of course, substituents having values that fall within the above range when measured on the basis of the Hammett""s rule even if they are unknown in literature.
Practical examples of R11 and R12, as the electron attractive group with a "sgr"p value of 0.20 to 1.0, are an acyl group, acyloxy group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl group substituted by at least two halogen atoms, alkoxy group substituted by at least two halogen atoms, aryloxy group substituted by at least two halogen atoms, alkylamino group substituted by at least two halogen atoms, alkylthio group substituted by at least two halogen atoms, aryl group substituted by another electron attractive group with a "sgr"p value of 0.20 or more, heterocyclic group, chlorine atom, bromine atom azo group, and selenocyanate group. Of these substituents, those capable of further having substituents can further have substitutes to be enumerated later for R13.
The aliphatic portion of an aliphatic oxycarbonyl group can be straight-chain, branched-chain, or cyclic and can be saturated or can contain an unsaturated bond. This aliphatic oxycarbonyl group includes, e.g., alkoxycarbonyl, cycloalkoxycarbonyl, alkenyloxycarbonyl, alkinyloxycarbonyl, and cycloalkenyloxycarbonyl.
The "sgr"p values of representative electron attractive groups having a "sgr"p value of 0.2 to 1.0 are a bromine atom (0.23), chlorine atom (0.23), cyano group (0.66), nitro group (0.78), trifluoromethyl group (0.54), tribromomethyl group (0.29), trichloromethyl group (0.33), carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.43), acetyloxy group (0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), and sulfamoyl group (0.57). Each of the numbers in parenthesis is "sgr"p value.
R11 preferably represents a cyano group, aliphatic oxycarbonyl group (a 2- to 36-carbon, straight-chain or branched-chain alkoxycarbonyl group, aralkyloxycarbonyl group, alkenyloxycarbonyl group, or alkinyloxycarbonyl group, or a 3-to 36-carbon cycloalkoxycarbonyl group, or cycloalkenyloxycarbonyl group, e.g., methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, or 2,6-di-t-butyl-4-methylcylohexyloxycarbonyl); dialkylphosphono group (a 2- to 36-carbon dialkylphosphono group, e.g., diethylphosphono or dimethylphosphono); alkylsulfonyl or arylsulfonyl group (a 1- to 36-carbon alkylsulfonyl or arylsulfonyl group, e.g., a methanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, or p-toluenesulfonyl group); or fluorinated alkyl group (a 1- to 36-carbon fluorinated alkyl group, e.g., trifluoromethyl). R11 is particularly preferably a cyano group, aliphatic oxycarbonyl group, or fluorinated alkyl group, and most preferably, a cyano group.
R12 preferably represents an aliphatic oxycarbonyl group as enumerated above for R11; carbamoyl group (a 1- to 36-carbon carbamoyl group, e.g., diphenylcarbamoyl or dioctylcarbamoyl); sulfamoyl group (a 1- to 36-carbon sulfamoyl, e.g., dimethylsulfamoyl or dibutylsulfamoyl); dialkylphosphono group enumerated above for R11; diarylphosphono group (a 12- to 50-carbon diarylphosphono group, e.g., diphenylphosphono or di(p-tolyl)phosphono). R12 is particularly preferably a group represented by the following formula (1). 
wherein each of R1xe2x80x2 and R2xe2x80x2 represents an aliphatic group, e.g., a 1- to 36-carbon, straight-chain or branched-chain alkyl group, aralkyl group, alkenyl group, alkinyl group, cycloalkyl group, or cycloalkenyl group, and more specifically, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl, or cyclohexyl. Each of R3xe2x80x2, R4xe2x80x2, and R5xe2x80x2 represents a hydrogen atom or aliphatic group. Examples of the aliphatic group are those enumerated above for R1xe2x80x2 and R2xe2x80x2. Each of R3xe2x80x2, R4xe2x80x2, and R5xe2x80x2 is preferably a hydrogen atom.
W represents a non-metallic atomic group required to form a 5- to 8-membered ring. This ring may be substituted, may be a saturated ring, or can have an unsaturated bond. A non-metallic atom is preferably a nitrogen atom, oxygen atom, sulfur atom, or carbon atom, and more preferably, a carbon atom.
Examples of a ring formed by W are a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, piperazine ring, oxane ring, and thiane ring. These rings can be substituted by the substituents described above.
A ring formed by W is preferably a cyclohexane ring which may be substituted, and most preferably, a cyclohexane ring whose 4-position is substituted by a 1- to 36-carbon alkyl group (which may be substituted by a substituent represented by R13 described below).
R13 represents a substituent. Examples are those enumerated above for R1 in formula (MC-I). R13 is preferably an alkoxy group, acylamino group, aliphatic group, or aryl group. These groups may be substituted by the substituents enumerated for R13.
Y represents a hydrogen atom or a group which splits off when the coupler reacts with the oxidized form of an aromatic primary amine color developing agent. When Y represents a split-off group, examples are those enumerated above in the explanation of X in formula (MC-I).
Y is preferably a hydrogen atom, halogen atom, aryloxy group, heterocyclic acyloxy group, dialkylphosphonooxy group, arylcarbonyloxy group, arylsulfonyloxy group, alkoxycarbonyloxy group, or carbamoyloxy group. Also, the split-off group or a compound released from the split-off group preferably has a property of further reacting with the oxidized form of an aromatic primary amine color developing agent. For example, the split-off group is a non-color-generating coupler, hydroquinone derivative, aminophenol derivative, sulfonamidophenol derivative.
In a coupler represented by formula (CC-I), a group represented by R12 or R13 can contain a coupler moiety represented by formula (CC-I) to form a polymer which is a dimer or a higher-order polymer (whose polymerization degree is preferably 50 to 10,000, more preferably 100 to 5,000, or a group represented by R12 or R13 can contain a polymeric chain to form a homopolymer or a copolymer. A typical example of a homopolymer or copolymer containing a polymeric chain is a homopolymer or copolymer of an addition polymer of ethylene type unsaturated compound having a coupler moiety represented by formula (CC-I). One or more types of cyan-generating repeating units having a coupler moiety represented by formula (CC-I) may be contained in the polymer. A copolymer can contain, as copolymerization components, one or more types of non-color-generating ethylene type monomers which do not couple with the oxidized product of an aromatic primary amine color developing agent such as acrylate, methacrylate, or maleate.
Practical examples of a coupler represented by formula (CC-I) will be presented below. However, the present invention is not restricted to these examples. 
The compound represented by formula (CC-I) of the present invention can be synthesized by known methods, e.g., methods described in J.C.S., 1961, page 518, J.C.S., 1962, page 5,149, Angew. Chem., Vol. 72, page 956 (1960), and Berichte, Vol. 97, page 3,436 (1964), and literature or similar methods cited in these literature.
Couplers bnn(which give maximum densities of 3.0 or more of yellow, magenta, and cyan of a color image after color development (the same shall apply hereinafter)) of the present invention can be introduced to a photosensitive material by various known dispersion methods. Of these methods, an oil-in-water dispersion method is preferable in which a coupler is dissolved in a high-boiling organic solvent (used in combination with a low-boiling solvent where necessary), the solution is dispersed by emulsification in an aqueous gelatin solution, and the dispersion is added to a silver halide emulsion.
Examples of the high-boiling solvent used in this oil-in-water dispersion method are described in, e.g., U.S. Pat. No. 2,322,027, the disclosure of which is incorporated herein by reference. Practical examples of steps, effects, and impregnating latexes of a latex dispersion method as one polymer dispersion method are described in, e.g., U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-B-53-41091, and EP029104. Dispersion using an organic solvent-soluble polymer is described in PCT International Publication W088/00723.
Examples of the high-boiling solvent usable in the abovementioned oil-in-water dispersion method are phthalic acid esters (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl)iso phthalate, and bis(1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, and di-2-ethylhexylphenyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, 2,4-dichloro benzoate, dodecyl benzoate, and 2-ethylhexyl-p-hydroxy benzoate), amides (e.g., N,N-diethyldodecaneamide and N,N-diethyllaurylamide), alcohols and phenols (e.g., isostearylalcohol and 2,4-di-tert-amylphenol), aliphatic esters (e.g., dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanate, tributyl citrate, diethyl azelate, isostearyl lactate, and trioctyl tosylate), aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (paraffins containing 10% to 80% of chlorine), trimesic acid esters (e.g., tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (e.g., 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, and 4-(4-dodecyloxyphenylsulfonyl)phenol), carboxylic acids (e.g., 2-(2,4-di-tert-amylphenoxy)butyric acid and 2-ethoxyoctanedecanic acid), and alkylphosphoric acids (e.g., di-(2-ethylhexyl)phosphoric acid and diphenylphosphoric acid). In addition to the above high-boiling solvents, compounds described in, e.g., JP-A-6-258803 can also be preferably used as high-boiling solvents.
Of these compounds, phosphoric acid esters are preferable, and the combination of phosphoric acid esters with alcohols or phenols is also preferable.
The weight ratio of a high-boiling organic solvent to a coupler of the present invention is preferably 0 to 2.0, more preferably, 0 to 1.0, and most preferably, 0 to 0.5.
As a co-solvent, it is also possible to use an organic solvent (e.g., ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide) having a boiling point of 30xc2x0 C. to about 160xc2x0 C.
The content of a coupler of the present invention in a photosensitive material is 0.01 to 10 g, preferably 0.1 g to 2 g per m2. The content is 1xc3x9710xe2x88x923 to 1 mol, preferably 2xc3x9710xe2x88x923 to 3xc3x9710xe2x88x921 mol per mol of a silver halide in the same photosensitive emulsion layer.
When a photosensitive layer has a unit configuration including two or more photosensitive emulsion layers differing in speed, the coupler content of the present invention per mol of a silver halide is preferably 2xc3x9710xe2x88x923 to 1xc3x9710xe2x88x921 mol in a low-speed layer and 3xc3x9710xe2x88x922 to 3xc3x9710xe2x88x921 mol in a high-speed layer.
The magenta-generating, 2-equivalent coupler of the present invention and the coupler represented by formula (MC-I) are preferably added to a green-photosensitive emulsion layer. Also, a cyan-generating, 2-equivalent coupler of the present invention and a coupler represented by formula (CC-I) are preferably added to a red-sensitive emulsion layer.
In the present invention, the 2-equivalent coupler or a coupler represented by formula (MC-I) or (CC-I) is preferably contained. Although another coupler can also be used together with these couplers, the results become more preferable as the ratio of a color dye arising from the coupler of the present invention in the contribution to the total density of dyes which form substantially the same color increases. More specifically, the amount is such that the 2-equivalent coupler or a coupler represented by formula (MC-I) or (CC-I) preferably occupies 30 mol % or more, more preferably 50 mol % or more, much more preferably 70 mol % or more among the couplers giving substantially the same color.
The photosensitive material of the present invention can also contain a competing compound (a compound which competes with an image forming coupler to react with the oxidized form of an anomatic primary amine color developing agent and which does not form any dye image). Examples of this competing coupler are reducing compounds such as hydroquinones, catechols, hydrazines, and sulfonamidophenols, and compounds which couple with the oxidized form of an anomatic primary amine color developing agent but do not substantially form a color image (e.g., colorless compound-forming couplers disclosed in German Patent No. 1,155,675, British Patent No. 861,138, and U.S. Pat. Nos. 3,876,428 and 3,912,513, the disclosures of which are incorporated herein by reference, and flow-out couplers disclosed in JP-A-6-83002, the disclosure of which is incorporated herein by reference).
The competing compound is preferably added to a photosensitive emulsion layer containing the magenta coupler of the present invention or a non-photosensitive layer. The competing compound is particularly preferably added to a photosensitive emulsion layer containing a coupler of the present invention. The content of a competing compound is 0.01 to 10 g, preferably 0.10 to 5.0 g per m2 of a photosensitive material. The content is 1 to 1,000 mol %, preferably 20 to 500 mol % with respect to a coupler of the present invention.
In a photosensitive material of the present invention, a photosensitive unit comprising emulsion layers sensitive to the same color but different in speed can have a non-color-generating interlayer. Additionally, this interlayer preferably contains a compound selectable as the aforementioned competing compound.
To prevent deterioration of the photographic properties caused by formaldehyde gas, a photosensitive material of the present invention preferably contains a compound described in U.S. Pat. Nos. 4,411,987 or 4,435,503, which can react with and fix formaldehyde gas.
A photosensitive material of the present invention need only have at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer on a support. Although a support is preferably coated with these layers in this order from the farthest one from the support, the order can also be changed.
In the present invention, it is preferable to form red-, green-, and blue-sensitive silver halide emulsion layers in this order from the closest one to a support. Each color-sensitive layer preferably has a unit configuration including two or more photosensitive emulsion layers different in sensitivity. More preferably, each color-sensitive layer has a three-layered unit configuration including three photosensitive emulsion layers, i.e., low-, medium-, and high-speed layers formed in this order from the closest one to a support.
In the present invention, silver halide grains having substantially no photosensitivity besides photosensitive silver halide are used in a photosensitive emulsion layer, an interlayer between two photosensitive emulsion layers and/or an interlayer between a photosensitive emulsion layer closest to a support and the support. This enhances the effect of improving processing nonuniformity.
In the present invention, xe2x80x9chaving substantially no photosensitivityxe2x80x9d is defined that the relative sensitivity to photosensitive silver halide having the lowest sensitivity in a photosensitive material is 1/100 or less (more preferably, 1/1,000 or less).
The silver halide emulsion grains having substantially no photosensitivity used in the invention are preferably silver bromide, silver iodobromide, silver chloride, silver iodide, silver bromochloroiodide, or silver chlorobromide, and more preferably, silver bromide, silver iodide, or silver iodobromide, having an average equivalent-sphere diameter of 0.02 to less than 0.15 xcexcm (more preferably, 0.03 to 0.10 xcexcm). When the silver halide emulsion grains are silver iodobromide, the silver iodide content is preferably 1 to 20 mol %.
The surface or the interior of the silver halide grain having substantially no photosensitivity may or may not be fogged. In the present invention, the silver halide grain is unfogged silver bromide, silver iodide, or silver iodobromide containing 1% to 20% of silver iodide. The average equivalent-sphere grain size is preferably 0.03 to 0.10 xcexcm.
When the silver halide fine grains having substantially no photosensitivity are added to a photosensitive emulsion layer, the addition amount is preferably 1% to 30%, and more preferably, 1% to 15%, as a silver molar ratio, with respect to the total silver halide in the layer.
When the silver halide fine grains having substantially no photosensitivity are added to an interlayer, the silver amount is preferably 1 mg to 1 g, and more preferably, 10 mg to 0.3 g per m2 of a photosensitive material. When the grains are added to an interlayer, this interlayer is preferably positioned between two photosensitive emulsion layers or between a support and a photosensitive emulsion layer closest to the support. More preferably, in a photosensitive material in which photosensitive emulsion layers are arranged in the order of red-, green-, and blue-sensitive layers from the closest one to a support, this interlayer is positioned between the green- and red-sensitive layers or between the support and the red-sensitive layer.
In the present invention, the silver halide grains are preferably unfogged non-photosensitive silver bromide or silver iodobromide (the silver iodide content is preferably 1% to 20%, and more preferably, 1% to 10%). The silver halide grains are preferably used together with a photosensitive emulsion within the range of 1% to 15% as a molar ratio with respect to the total silver halide in a photosensitive emulsion layer containing the grains.
Photosensitive silver halide emulsions to be contained in a photosensitive material of the present invention will be described below.
Photosensitive silver halide grains for use in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver iodochloride, silver iodobromide, or silver bromochloroiodide. A silver halide grain can also contain another silver salt, such as silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate, or organic acid silver, as another grain or as a portion of the grain. In the present invention, silver iodobromide or silver bromochloroiodide is preferable. The silver iodide content is preferably 0.5 to 30 mol %, more preferably, 1 to 10 mol %, and most preferably 1 to 5 mol %.
Photosensitive silver halide grains for use in the present invention can be selected in accordance with the intended use. Examples are a regular crystal not containing a twin plane and crystals explained in Japan Photographic Society ed., The Basis of Photographic Engineering, Silver Salt Photography (CORONA PUBLISHING CO., LTD. (1979)), page 163, such as a single twinned crystal containing one twin plane, a parallel multiple twinned crystal containing two or more parallel twin planes, and a nonparallel multiple twinned crystal containing two or more nonparallel twin planes. A method of mixing grains having different shapes is disclosed in U.S. Pat. No. 4,865,964, and this method can be selected as needed. In the case of a regular crystal, it is possible to use a cubic grain constituted by (100) faces, an octahedral grain constituted by (111) faces, or a dodecahedral grain constituted by (110) faces disclosed in JP-B-55-42737 or JP-A-60-222842.
It is also possible to use, in accordance with the intended use, an (h11) face grain represented by a (211) face grain, an (hh1) face grain represented by a (331) face grain, an (hk0) face grain represented by a (210) face grain, or an (hk1) face grain represented by a (321) face grain, as reported in Journal of Imaging Science, Vol. 30, page 247, 1986, although the preparation method requires some improvements. A grain having two or more different faces, such as a tetradecahedral grain having both (100) and (111) faces, a grain having (100) and (110) faces, or a grain having (111) and (110) faces, can also be used in accordance with the intended use.
A value obtained by dividing the equivalent-circle diameter of the projected area of a grain by the thickness of that grain is called an aspect ratio that defines the shape of a tabular grain.
Tabular grains having aspect ratios higher than 1 are preferably used in the present invention. Particularly favorable results can be obtained when tabular grains having an aspect ratio of 2 or more account for 50% or more (more preferably 70% or more) as a silver ratio of all photosensitive silver halide grains.
Tabular grains can be prepared by the methods described in, e.g., Cleve, Photography Theory and Practice (1930), page 131; Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257, (1970); and U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
The shape of a tabular grain can be selected from, e.g., a triangle, hexagon, and circle. A regular hexagon having six substantially equal side length as described in U.S. Pat. No. 4,797,354 is a preferred form.
An equivalent-circle diameter of a projected area is often used as the grain size of a tabular grain. To improve the image quality, grains with an average diameter of 0.6 xcexcm or smaller such as described in U.S. Pat. No. 4,748,106 are preferable. Also, as the shape of a tabular grain, limiting the grain thickness to 0.5 xcexcm or less, more preferably, 0.3 xcexcm or less is preferable to improve the sharpness. Grains described in JP-A-63-163451 in which the grain thickness and the distance between twin planes are defined are also preferable.
More desirable results can sometimes be obtained when monodisperse tabular grains with a narrow grain size distribution are used. U.S. Pat. No. 4,797,354 and JP-A-2-838 describe methods of manufacturing monodisperse hexagonal tabular grains with high tabularity. EP514,742 describes a method of manufacturing tabular grains having a grain size distribution variation coefficient of less than 10% by using a polyalkyleneoxide block copolymer. The use of these tabular grains in the present invention is preferred. Grains with a grain thickness variation coefficient of 30% or less, i.e., with a high thickness uniformity, are also preferred.
The sensitive silver halide emulsion of the present invention is preferably a monodisperse emulsion having a narrow grain size distribution. More specifically, it is desirable to use a monodisperse emulsion having a size distribution with an equivalent-sphere diameter variation coefficient of preferably 25% or less, more preferably, 20% or less, and much more preferably, 15% or less.
In silver halide photosensitive materials of the present invention and silver halide photosensitive emulsions used therein, it is generally possible to use various techniques and inorganic and organic materials described in Research Disclosure Nos. 308119 (1989), 37038 (1995), and 40145 (1997).
In addition, and more specifically, techniques and inorganic and organic materials usable in color photosensitive materials of the present invention can be applied are described in portions of EP436,938A2 and patents cited below, the disclosures of which are incorporated herein by reference.